CN109126835A - Photochemical catalyst La3+The method of/BiOI and bisphenol AF of degrading - Google Patents
Photochemical catalyst La3+The method of/BiOI and bisphenol AF of degrading Download PDFInfo
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- CN109126835A CN109126835A CN201810834212.8A CN201810834212A CN109126835A CN 109126835 A CN109126835 A CN 109126835A CN 201810834212 A CN201810834212 A CN 201810834212A CN 109126835 A CN109126835 A CN 109126835A
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- bisphenol
- bioi
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- degradation
- photochemical catalyst
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- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 67
- 230000000593 degrading effect Effects 0.000 title claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 65
- 230000015556 catabolic process Effects 0.000 claims abstract description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- -1 persulfuric acid hydrogen salt Chemical class 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 230000005855 radiation Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 59
- 238000002156 mixing Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 12
- 238000004064 recycling Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 231100000734 genotoxic potential Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a kind of photochemical catalyst La3+The method of/BiOI and bisphenol AF of degrading, belong to water-treatment technology field.The present invention provides a kind of novel photocatalyst La to solve the problems, such as that existing bisphenol AF treatment process treatment effeciency is low, complex process, take time and effort3+/ BiOI, and utilize persulfuric acid hydrogen salt and photochemical catalyst La3+/ BiOI degradation bisphenol AF, degradation step includes: to mix persulfuric acid hydrogen salt with the aqueous solution containing bisphenol AF, regulation system pH, and photochemical catalyst La is then added3+/ BiOI after stirring, through radiation of visible light, that is, realizes the degradation of bisphenol AF.The method of the present invention is easy to operate, and degradation by-products are nontoxic；It is reacted under normal temperature and pressure, visible light, saves the energy, significantly reduce cost；Photochemical catalyst can be easier to recycle and regenerate；Have good removal rate up to 85% or more bisphenol AF in water.
Description
Technical field
The invention belongs to water-treatment technology fields, and in particular to the degradation of a kind of photochemical catalyst La3+/BiOI and bisphenol AF
Method.
Background technique
Bisphenol AF (hexafluoro bisphenol-a, BPAF, molecular formula C15H10F6O2) it is widely used as the crosslinking agent and sulphur of fluoroelastomer
The remodeling monomer of agent, multiple polymers such as polyimides, polyamide, polyester, poly- carbon and other particular polymers.However, double
Phenol AF is a kind of typical incretion interferent as bisphenol-A with other bisphenols, and fluoro organic matter is often more
Hardly possible is decomposed, and has higher stability and persistence in the environment.As emerging environmental contaminants, BPAF is in various environment
It is detected in matrix, is carried out in organism by a variety of route of exposure, there are potential risks to ecological and human health.In recent years
Come, the genotoxic potential and endocrine disrupting of BPAF have become the research emphasis of field of environmental improvement, how to remove in environment
Bisphenol AF also become hot issue.
Conventional physical treatment process, method of chemical treatment and biological treatment all cannot effectively realize the degradation of bisphenol AF.Mesh
Before, rarely have the report to bisphenol AF degradation.In recent years, the high-level oxidation technology based on potentiometric titrations is widely used in dirty useless
In the research of water process.The persulfate of the techniques such as ultraviolet light (UV), heat, metal ion activation, intramolecule peroxide bridge can
Potentiometric titrations are broken to form, oxidability is suitable with hydroxyl radical free radical, and has selectivity is stronger, half-life period is longer etc.
Advantage.On the other hand using solar energy photocatalytic degradation Industry Waste Organic substance in water is high with degradation efficiency, salinity is high, operation
The advantages that convenient, easily controllable, without secondary pollution, has tremendous expansion potentiality.Existing optically catalytic TiO 2 degradation bis-phenol
AF method carries out photocatalytic degradation to bisphenol AF using titania solution, but this method degradation time is long, and treating capacity is lower, is limited
Make more, operating procedure complexity, higher cost.
CN107050732A discloses a kind of method using white-rot fungi crude enzyme liquid degradation bisphenol AF, but this method is first
More complicated operation preparation white-rot fungi crude enzyme liquid is needed, and is only capable of the bisphenol AF solution of processing low concentration, when reaction
Between it is long, application range is small.
It would therefore be highly desirable to the method for developing a kind of novel photocatalyst for bisphenol AF of degrading and degradation bisphenol AF.
Summary of the invention
The present invention mentions to solve the problems, such as that existing bisphenol AF treatment process treatment effeciency is low, complex process, take time and effort
For a kind of method of bisphenol AF of degrading, method includes the following steps:
A, persulfuric acid hydrogen salt is mixed with the aqueous solution containing bisphenol AF, regulation system pH obtains mixed solution；
B, by photochemical catalyst La3+/ BiOI is added in mixed solution obtained by step A, after stirring, obtains suspension；
C, suspension obtained by step B realizes the degradation of bisphenol AF through radiation of visible light.
Wherein, in the method for degradation bisphenol AF described above, in step A, the persulfuric acid hydrogen salt and contain bisphenol AF
Aqueous solution mass ratio be 1:1000~10000.
Preferably, in the method for degradation bisphenol AF described above, in step A, the persulfuric acid hydrogen salt and contain bis-phenol
The mass ratio of the aqueous solution of AF is 1:5000~8000.
Wherein, in the method for degradation bisphenol AF described above, in step A, the persulfuric acid hydrogen salt be potassium hydrogen persulfate,
At least one of hydrogen persulfate ammonium, hydrogen persulfate sodium or hydrogen persulfate calcium.
Wherein, in the method for degradation bisphenol AF described above, in step A, the aqueous solution containing bisphenol AF it is dense
Degree is 1~1000mg/L.
Wherein, in the method for degradation bisphenol AF described above, in step A, the persulfuric acid hydrogen salt and contain bisphenol AF
Aqueous solution mixing when mixing speed be 160r/min~250r/min.
Wherein, in the method for degradation bisphenol AF described above, in step A, the persulfuric acid hydrogen salt and contain bisphenol AF
Aqueous solution mixing when mixing time be 20min~45min.
Wherein, in the method for degradation bisphenol AF described above, in step A, the regulation system pH is regulation system pH
To 6.5~7.5.
Preferably, in the method for degradation bisphenol AF described above, in step A, the operation of the regulation system pH are as follows:
Mixing speed be 150r/min~200r/min under conditions of, into system be added 0.1mol/L~100mol/L inorganic acid or
The inorganic alkali solution of 0.1mol/L~100mol/L, regulation system pH to 6.5~7.5.
Preferably, in the method for degradation bisphenol AF described above, in step A, the inorganic acid is hydrochloric acid or perchloric acid.
Preferably, in the method for degradation bisphenol AF described above, in step A, the inorganic base is sodium hydroxide or hydrogen
Potassium oxide.
Wherein, in the method for degradation bisphenol AF described above, in step B, the photochemical catalyst La3+The addition of/BiOI
Amount is the aqueous solution that 0.01~50.0g/L contains bisphenol AF.
Preferably, in the method for degradation bisphenol AF described above, in step B, the photochemical catalyst La3+/ BiOI's adds
Entering amount is the aqueous solution that 0.1~10g/L contains bisphenol AF.
Wherein, in the method for degradation bisphenol AF described above, in step B, the speed of the stirring be 160r/min~
250r/min。
Wherein, in the method for degradation bisphenol AF described above, in step B, the time of the stirring be 5min~
10min。
Wherein, in the method for degradation bisphenol AF described above, in step C, the wavelength of the visible light is 420~
700nm。
Wherein, in the method for degradation bisphenol AF described above, in step C, the light source power of the visible light is 100W
~1000W.
Preferably, in the method for degradation bisphenol AF described above, in step C, the light source power of the visible light is
300W~1000W.
Wherein, in the method for degradation bisphenol AF described above, in step C, the time of the irradiation be 10min~
240min。
Wherein, it in the method for degradation bisphenol AF described above, in step C, irradiates while being stirred, mixing speed is
150r/min~200r/min.
Wherein, in the method for degradation bisphenol AF described above, further include filtration step after bisphenol AF degradation, recycle light
Catalyst La3+/BiOI。
Wherein, in the method for degradation bisphenol AF described above, the photochemical catalyst La3+/ BiOI is prepared by following methods
It obtains:
A, by Bi (NO3)3·5H2O is dissolved in dehydrated alcohol, obtains solution a；KI is soluble in water, obtain solution b；By solution b
It is added in solution a, obtains mixed liquor；
B, by La (NO3)3·6H2O is added to absolute ethanol, and after agitated mixing, ultrasound, obtains La (NO3)3·6H2O's is equal
One state solution；
C, by La (NO3)3·6H2The uniform state solution of O is added in mixed liquor obtained by step a, after mixing, moves to height
It is reacted in pressure reaction kettle, end of reaction, filtering, drying obtain photochemical catalyst La3+/BiOI。
The present invention also provides a kind of novel photocatalyst La3+/ BiOI, is prepared by following methods:
A, by Bi (NO3)3·5H2O is dissolved in dehydrated alcohol, obtains solution a；KI is soluble in water, obtain solution b；By solution b
It is added in solution a, obtains mixed liquor；
B, by La (NO3)3·6H2O is added to absolute ethanol, and after agitated mixing, ultrasound, obtains La (NO3)3·6H2O's is equal
One state solution；
C, by La (NO3)3·6H2O solution is added in mixed liquor obtained by step a, after mixing, moves to autoclave
In reacted, end of reaction is filtering, dry, obtains photochemical catalyst La3+/BiOI。
Wherein, photochemical catalyst La described above3+In/BiOI, in step a, when preparing solution a, the Bi (NO3)3·
5H2The dosage of O is 0.01~0.1g/mL dehydrated alcohol.
Wherein, photochemical catalyst La described above3+In/BiOI, in step a, when preparing solution a, by Bi (NO3)3·5H2O
The mixing speed for being dissolved in dehydrated alcohol is 160r/min~250r/min, and mixing time is 30~45min.
Wherein, photochemical catalyst La described above3+In/BiOI, in step a, when preparing solution b, the dosage of the KI is
0.01~0.05g/mL water.
Wherein, photochemical catalyst La described above3+In/BiOI, in step a, after solution a is added in solution b, in 160r/
30~60min is stirred under min~250r/min.
Wherein, photochemical catalyst La described above3+In/BiOI, in step b, the La (NO3)3·6H2The dosage of O is
0.3~1.5g/mL dehydrated alcohol.
Wherein, photochemical catalyst La described above3+In/BiOI, in step b, the speed being stirred is 160r/
Min~250r/min, time are 30min~60min.
Wherein, photochemical catalyst La described above3+In/BiOI, in step b, time of the ultrasound be 5min~
10min。
Wherein, photochemical catalyst La described above3+In/BiOI, in step c, the uniformly mixed operation are as follows:
30min~60min is stirred under 160r/min~250r/min.
Wherein, photochemical catalyst La described above3+In/BiOI, in step c, the temperature of the reaction is 160 DEG C~180
DEG C, the time is 16h~for 24 hours.
Wherein, photochemical catalyst La described above3+In/BiOI, in step c, the temperature of the drying is 60 DEG C~80 DEG C,
Time is 8h~12h.
Wherein, photochemical catalyst La described above3+In/BiOI, the Bi (NO3)3·5H2O, KI and La (NO3)3·6H2O
Molar ratio be 1~2:1~2:1~2.
The beneficial effects of the present invention are:
Present invention firstly provides a kind of novel photocatalyst La3+/ BiOI, for bisphenol AF of degrading.The present invention utilized
Sulfate and photochemical catalyst La3+/ BiOI is able to achieve the efficient degradation of bisphenol AF, to bisphenol AF in water at normal temperatures and pressures
For removal rate up to 85% or more, degradation by-products are nontoxic, save the energy；Utilize catalyst La3+/ BiOI degradation bisphenol AF,
There can be preferred response to visible light, there is extensive practical value；And photochemical catalyst La of the invention3+/ BiOI can
Light recycling and reusing, greatly reduces cost.
Specific embodiment
Specifically, using the method for degradation bisphenol AF, method includes the following steps:
A, persulfuric acid hydrogen salt is mixed with the aqueous solution containing bisphenol AF, regulation system pH obtains mixed solution；
B, by photochemical catalyst La3+/ BiOI is added in mixed solution obtained by step A, after stirring, obtains suspension；
C, suspension obtained by step B realizes the degradation of bisphenol AF through radiation of visible light.
The La that the present invention uses3+/ BiOI can use sunlight and urge as a kind of newer conductor photocatalysis material
Change, has many advantages, such as non-toxic, high stability, be a kind of environment-friendly type semiconductor catalyst of function admirable, there is wide answer
Use prospect.La3+/ BiOI has certain catalytic activity under visible light conditions, compensates for TiO2Equivalence classes catalyst can not
Under visible light the shortcomings that photocatalysis degradation organic contaminant, and improve the removal rate of pollutant.
The principle of invention:
4h++2H2O-→4H++·OH (4)
In photochemical catalyst La in the present invention3+The surface /BiOI under visible light illumination, positioned at the photoelectron transition of forbidden band, shape
At hole-electron pair (h+-e- CB).La in reaction system3+The photoelectron and the HSO in persulfuric acid hydrogen salt on the surface /BiOI5 -Or
SO5 2-Electronics transfer occurs, so that persulfuric acid hydrogen radical is cracked into SO4 -With OH-；In addition, the O in solution2In photoelectron
Under effect, the superoxide radical reactive oxygen species with strong oxidizing property have been similarly generated, have accelerated the purification speed of bisphenol AF molecule
Rate；On the other hand photochemical catalyst La is rested on3+The hole on the surface /BiOI has strong oxidizing property, and can further speed up target has
The oxidative degradation of machine object.
In the method for the present invention step A, the mass ratio of the persulfuric acid hydrogen salt and the aqueous solution containing bisphenol AF is 1:1000
~10000；Preferably 1:5000~8000；The persulfuric acid hydrogen salt be potassium hydrogen persulfate, hydrogen persulfate ammonium, hydrogen persulfate sodium or
At least one of hydrogen persulfate calcium.
The method of the present invention can effectively deal with the aqueous solution that bisphenol AF concentration is 1~1000mg/L, can answer in various environment
With applied widely.
For the abundant dissolution for guaranteeing persulfuric acid hydrogen salt, it can be sufficiently mixed with bisphenol AF, be conducive to subsequent addition photocatalysis
Degradation reaction carries out after agent, and in step A, mixing speed when control persulfuric acid hydrogen salt is mixed with the aqueous solution containing bisphenol AF is
160r/min~250r/min, mixing time are 20min~45min.
After persulfuric acid hydrogen salt is mixed with the aqueous solution containing bisphenol AF, the possible slant acidity of system, it is also possible to meta-alkalescence, at this time
It needs for system pH to be adjusted to 6.5~7.5, guarantees that reaction condition is neutrality.Preferably, low whipping speed be 150r/min~
The nothing of 0.1mol/L~100mol/L is added into system when system meta-alkalescence by regulation system pH under conditions of 200r/min
Machine acid (preferably hydrochloric acid or perchloric acid) regulation system pH to 6.5~7.5；When system slant acidity, 0.1mol/ is added into system
Inorganic base (preferably sodium hydroxide or potassium hydroxide) solution regulation system pH to 6.5~7.5 of L~100mol/L.
The method of the present invention can efficiently remove the bisphenol AF in water, photochemical catalyst La3+/ BiOI dosage is few, described in step B
Photochemical catalyst La3+The additional amount of/BiOI is the aqueous solution that 0.01~50.0g/L contains bisphenol AF；Preferably, the photochemical catalyst
La3+The additional amount of/BiOI is the aqueous solution that 0.1~10g/L contains bisphenol AF.
To guarantee that photochemical catalyst can be sufficiently mixed with bisphenol AF, in step B, the speed of stirring for 160r/min~
250r/min, and controlling mixing time is 5min~10min, to guarantee reaction time and treatment effect.
The degradation of bisphenol AF can be realized in the method for the present invention under visible light illumination, and the power for providing the light source of visible light is
100W~1000W；Preferably 300W~1000W；The wavelength of visible light is 420~700nm.
The method of the present invention degradation time is short, saves the energy, irradiates 10min~240min under visible light, can be completed double
The degradation of phenol AF.
After bisphenol AF degradation, the basic no consumption of photochemical catalyst, therefore can be filtered, recycle photochemical catalyst La3+/ BiOI,
The photochemical catalyst La of recycling3+/ BiOI can be re-used for the degradation of bisphenol AF, further reduce the cost.
Photochemical catalyst La used in the present invention3+/ BiOI can be prepared by following methods:
A, by Bi (NO3)3·5H2O is dissolved in dehydrated alcohol, obtains solution a；KI is soluble in water, obtain solution b；By solution b
It is added in solution a, obtains mixed liquor；
B, by La (NO3)3·6H2O is added to absolute ethanol, and after agitated mixing, ultrasound, obtains La (NO3)3·6H2O's is equal
One state solution；
C, by La (NO3)3·6H2The uniform state solution of O is added in mixed liquor obtained by step a, after mixing, moves to height
It is reacted in pressure reaction kettle, end of reaction, filtering, drying obtain photochemical catalyst La3+/BiOI。
More specifically, the photochemical catalyst La used in the present invention3+/ BiOI can be prepared by following methods:
A, by Bi (NO3)3·5H2O is dissolved in dehydrated alcohol, obtains solution a；KI is soluble in water, obtain solution b；By solution b
It is added in solution a, 30~60min is stirred at 160r/min~250r/min, obtains mixed liquor；When preparing solution a, the Bi
(NO3)3·5H2The dosage of O is 0.01~0.1g/mL dehydrated alcohol；When preparing solution a, by Bi (NO3)3·5H2O is dissolved in anhydrous
The mixing speed of ethyl alcohol is 160r/min~250r/min, and mixing time is 30~45min；When preparing solution b, the use of the KI
Amount is 0.01~0.05g/mL water；
B, by La (NO3)3·6H2O is added to absolute ethanol, be stirred at 160r/min~250r/min 30min~
60min, then ultrasound 5min~10min, obtains La (NO3)3·6H2The uniform state solution of O；La (the NO3)3·6H2The dosage of O
For 0.3~1.5g/mL dehydrated alcohol；
C, by La (NO3)3·6H2The uniform state solution of O is added in mixed liquor obtained by step a, in 160r/min~250r/
It stirs 30min~60min under min to move in autoclave and reacted after mixing, end of reaction, filtering, drying,
Obtain photochemical catalyst La3+/BiOI；The temperature of the reaction is 160 DEG C~180 DEG C, and the time is 16h~for 24 hours；The temperature of the drying
It is 60 DEG C~80 DEG C, the time is 8h~12h；
Bi (the NO3)3·5H2O, KI and La (NO3)3·6H2The molar ratio of O is 1~2:1~2:1~2.
Below by test example and embodiment, invention is further described in detail, but does not therefore protect the present invention
Scope limitation is among the embodiment described range.
Photochemical catalyst La in the embodiment of the present invention3+/ BiOI is prepared by following methods:
A, 30mmol (14.55g) Bi (NO is taken3)3·5H2O is dissolved in 300mL dehydrated alcohol, is stirred at 200r/min
45min obtains solution a；It takes the KI of 30mmol (4.98g) to be dissolved in 300mL pure water, obtains solution b；Solution b is slowly added dropwise into molten
In liquid a, 60min is stirred at 200r/min, obtains mixed liquor, mixed liquor is in the suspended state of bronzing；
B, 12.99g La (NO is taken3)3·6H2O is added in 200mL dehydrated alcohol, is stirred at 250r/min
45min, then ultrasound 10min, obtains La (NO3)3·6H2The uniform state solution of O；
C, by La (NO3)3·6H2The uniform state solution of O is added in mixed liquor obtained by step a, stirs at 200r/min
60min is moved in 1L autoclave after mixing, is reacted at 180 DEG C for 24 hours, after reaction kettle is cooled to room temperature, filtering,
Filter cake dehydrated alcohol with deionized water repeated flushing 6~10 times, obtained solid moves in vacuum oven, in 80 DEG C of dryings
12h obtains 14.7g photochemical catalyst La3+/BiOI。
Embodiment 1
The present embodiment is using following methods degradation bisphenol AF, comprising the following steps:
A, potassium hydrogen persulfate 5mg is taken, the aqueous solution 100mL containing bisphenol AF that concentration is 30mg/L, in room gentle agitation
Speed mixes 30min under the conditions of being 200r/min, under conditions of then low whipping speed is 150r/min, is added into system
The perchloric acid of 0.1mol/L or the sodium hydroxide solution of 0.1mol/L, regulation system pH to 7.0 obtain mixed solution；
B, by 0.4g photochemical catalyst La3+/ BiOI is added in mixed solution obtained by step A, is in room temperature and mixing speed
20min is stirred under the conditions of 160r/min, obtains suspension；
C, the light source power for controlling visible light is 300W, by suspension obtained by step B wavelength be 420~700nm can
Light-exposed lower irradiation 30min, control mixing speed is 200r/min when irradiation, realizes the degradation of bisphenol AF, obtains removal bisphenol AF
Afterwards contain photochemical catalyst La3+The water of/BiOI, the degradation rate of bisphenol AF are 88%；
D, contain photochemical catalyst La after using aperture that will remove bisphenol AF for 0.45 μm of glass fibre membrane3+/ BiOI's
Water is filtered, and obtains the water of removal bisphenol AF and the photochemical catalyst La of recycling3+/BiOI。
Embodiment 2
The present embodiment is using following methods degradation bisphenol AF, comprising the following steps:
A, it takes potassium hydrogen persulfate 100mg, the aqueous solution 1000mL containing bisphenol AF that concentration is 30mg/L, in room temperature and stirs
It mixes under the conditions of speed is 200r/min and mixes 30min, under conditions of then low whipping speed is 180r/min, be added into system
The perchloric acid of 0.1mol/L or the sodium hydroxide solution of 0.1mol/L, regulation system pH to 6.5~7.5 obtain mixed solution；
B, by 5g photochemical catalyst La3+/ BiOI is added in mixed solution obtained by step A, is 200r/ in room temperature and mixing speed
30min is stirred under the conditions of min, obtains suspension；
C, the light source power for controlling visible light is 800W, in wavelength is 420nm~700nm's by suspension obtained by step B
Irradiate 90min under visible light, control mixing speed is 200r/min when irradiation, realizes the degradation of bisphenol AF, obtains removal bis-phenol
Contain photochemical catalyst La after AF3+The water of/BiOI, the degradation rate of bisphenol AF are 92%；
D, contain photochemical catalyst La after using aperture that will remove bisphenol AF for 0.45 μm of glass fibre membrane3+/ BiOI's
Water is filtered, and obtains the water of removal bisphenol AF and the photochemical catalyst La of recycling3+/BiOI。
Embodiment 3
The present embodiment is using following methods degradation bisphenol AF, comprising the following steps:
A, potassium hydrogen persulfate 1.5g is taken, the aqueous solution 10L containing bisphenol AF that concentration is 30mg/L, the gentle agitation speed in room
Degree mixes 30min under the conditions of being 200r/min, under conditions of then low whipping speed is 200r/min, is added into system
The perchloric acid of 0.1mol/L or the sodium hydroxide solution of 0.1mol/L, regulation system pH to 6.5~7.5 obtain mixed solution；
B, by 50g photochemical catalyst La3+/ BiOI is added in mixed solution obtained by step A, is in room temperature and mixing speed
45min is stirred under the conditions of 250r/min, obtains suspension；
C, the light source power for controlling visible light is 1000W, in wavelength is 420nm~700nm's by suspension obtained by step B
Irradiate 90min under visible light, control mixing speed is 150r/min when irradiation, realizes the degradation of bisphenol AF, obtains removal bis-phenol
Contain photochemical catalyst La after AF3+The water of/BiOI, the degradation rate of bisphenol AF are 95%；
D, contain photochemical catalyst La after using aperture that will remove bisphenol AF for 0.45 μm of glass fibre membrane3+/ BiOI's
Water is filtered, and obtains the water of removal bisphenol AF and the photochemical catalyst La of recycling3+/BiOI。
Comparative example 1
This comparative example uses titanium dioxide degradable bisphenol AF, specifically operates according to the following steps:
A, taking concentration is the aqueous solution 100mL containing bisphenol AF of 30mg/L, and low whipping speed is the condition of 200r/min
Under, the sodium hydroxide solution of the perchloric acid of addition 0.1mol/L or 0.1mol/L into system, regulation system pH to 6.5~7.5,
Obtain mixed solution；
B, by 0.5g photochemical catalyst TiO2It is added in mixed solution obtained by step A, is 250r/ in room temperature and mixing speed
30min is stirred under the conditions of min, obtains suspension；
C, the obtained suspension of step B is divided into two parts, portion irradiates 90min at a length of 280nm of ultraviolet light wave, ultraviolet
Light source power is 1000W, another is that 420~700nm irradiates 90min in the wavelength of visible light, it is seen that radiant power is
1000W；
Using the bisphenol AF in ultraviolet light and titanium dioxide degradable water, the removal rate of bisphenol AF is 80%, uses visible light
With the bisphenol AF in titanium dioxide degradable water, the removal rate of bisphenol AF is 5%.It proves to be only capable of using titanium dioxide as catalyst
There is preferable removal rate to bisphenol AF under ultraviolet light, under visible light poor effect.
Claims (9)
1. the method for bisphenol AF of degrading, comprising the following steps:
A, persulfuric acid hydrogen salt is mixed with the aqueous solution containing bisphenol AF, regulation system pH obtains mixed solution；
B, by photochemical catalyst La3+/ BiOI is added in mixed solution obtained by step A, after stirring, obtains suspension；
C, suspension obtained by step B realizes the degradation of bisphenol AF through radiation of visible light.
2. it is according to claim 1 degradation bisphenol AF method, it is characterised in that: in step A, the persulfuric acid hydrogen salt with
The mass ratio of aqueous solution containing bisphenol AF is 1:1000~10000.
3. the method for degradation bisphenol AF according to claim 1 or 2, it is characterised in that: in step A, at least meet following
One:
The persulfuric acid hydrogen salt is at least one of potassium hydrogen persulfate, hydrogen persulfate ammonium, hydrogen persulfate sodium or hydrogen persulfate calcium；
The concentration of the aqueous solution containing bisphenol AF is 1~1000mg/L；
Mixing speed when the persulfuric acid hydrogen salt is mixed with the aqueous solution containing bisphenol AF is 160r/min~250r/min；
Mixing time when the persulfuric acid hydrogen salt is mixed with the aqueous solution containing bisphenol AF is 20min~45min；
The regulation system pH is regulation system pH to 6.5~7.5；
The operation of the regulation system pH are as follows: under conditions of low whipping speed is 150r/min~200r/min, add into system
Enter the inorganic acid of 0.1mol/L~100mol/L or the inorganic alkali solution of 0.1mol/L~100mol/L, regulation system pH to 6.5
~7.5.
4. the method for degradation bisphenol AF according to claim 1, it is characterised in that: in step B, the photochemical catalyst La3+/
The additional amount of BiOI is the aqueous solution that 0.01~50.0g/L contains bisphenol AF.
5. the method for degradation bisphenol AF according to claim 1, it is characterised in that: in step B, the speed of the stirring is
160r/min~250r/min；The time of the stirring is 5min~10min.
6. the method for degradation bisphenol AF according to claim 1, it is characterised in that: in step C, at least meet following one
:
The wavelength of the visible light is 420~700nm；
The light source power of the visible light is 100W~1000W；
The time of the irradiation is 10min~240min；
It irradiates while being stirred, mixing speed is 150r/min~200r/min.
7. the method for described in any item degradation bisphenol AFs according to claim 1~6, it is characterised in that: after bisphenol AF degradation, also
Including filtration step, photochemical catalyst La is recycled3+/BiOI。
8. the method for described in any item degradation bisphenol AFs according to claim 1~7, it is characterised in that: the photochemical catalyst La3 +/ BiOI is prepared by following methods:
A, by Bi (NO3)3·5H2O is dissolved in dehydrated alcohol, obtains solution a；KI is soluble in water, obtain solution b；Solution b is added
In solution a, mixed liquor is obtained；
B, by La (NO3)3·6H2O is added to absolute ethanol, and after agitated mixing, ultrasound, obtains La (NO3)3·6H2The uniform state of O
Solution；
C, by La (NO3)3·6H2The uniform state solution of O is added in mixed liquor obtained by step a, after mixing, it is anti-to move to high pressure
It answers in kettle and is reacted, end of reaction, filtering, drying obtain photochemical catalyst La3+/BiOI。
9. photochemical catalyst La3+/ BiOI, it is characterised in that: be prepared by following methods:
A, by Bi (NO3)3·5H2O is dissolved in dehydrated alcohol, obtains solution a；KI is soluble in water, obtain solution b；Solution b is added
In solution a, mixed liquor is obtained；
B, by La (NO3)3·6H2O is added to absolute ethanol, and after agitated mixing, ultrasound, obtains La (NO3)3·6H2The uniform state of O
Solution；
C, by La (NO3)3·6H2The uniform state solution of O is added in mixed liquor obtained by step a, after mixing, it is anti-to move to high pressure
It answers in kettle and is reacted, end of reaction, filtering, drying obtain photochemical catalyst La3+/BiOI。
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| CN114160171A (en) * | 2021-11-10 | 2022-03-11 | 中国电建集团成都勘测设计研究院有限公司 | CeO2-La3+Preparation method of/BiOI composite material and method for removing sulfadiazine in water |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113697931A (en) * | 2021-09-07 | 2021-11-26 | 天津理工大学 | Self-doped bismuth tungstate (Bi)2.15WO6) Method for efficiently removing bisphenol A by Persulfate (PS) system |
| CN113697931B (en) * | 2021-09-07 | 2024-05-10 | 天津理工大学 | Self-doping bismuth tungstate (Bi)2.15WO6) Method for efficiently removing bisphenol A by Persulfate (PS) system |
| CN114160171A (en) * | 2021-11-10 | 2022-03-11 | 中国电建集团成都勘测设计研究院有限公司 | CeO2-La3+Preparation method of/BiOI composite material and method for removing sulfadiazine in water |
| CN115254152A (en) * | 2022-06-22 | 2022-11-01 | 中国科学技术大学苏州高等研究院 | Application of cobalt-doped bismuth oxybromide catalyst in selective oxidative degradation of pollutants |
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